EP1061108B1 - Low-staining adhesive sheets and method for removing resist material - Google Patents

Low-staining adhesive sheets and method for removing resist material Download PDF

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Publication number
EP1061108B1
EP1061108B1 EP00112397A EP00112397A EP1061108B1 EP 1061108 B1 EP1061108 B1 EP 1061108B1 EP 00112397 A EP00112397 A EP 00112397A EP 00112397 A EP00112397 A EP 00112397A EP 1061108 B1 EP1061108 B1 EP 1061108B1
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EP
European Patent Office
Prior art keywords
low
staining
adhesive sheet
molecular weight
pressure
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP00112397A
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German (de)
English (en)
French (fr)
Other versions
EP1061108A3 (en
EP1061108A2 (en
Inventor
Eiji c/o Nitto Denko Corporation Toyoda
Makoto c/o Nitto Denko Corporation Namikawa
Yoshio c/o Nitto Denko Corporation Terada
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Nitto Denko Corp
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Nitto Denko Corp
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Filing date
Publication date
Priority claimed from JP36778599A external-priority patent/JP4495813B2/ja
Priority claimed from JP2000011094A external-priority patent/JP4859005B2/ja
Application filed by Nitto Denko Corp filed Critical Nitto Denko Corp
Publication of EP1061108A2 publication Critical patent/EP1061108A2/en
Publication of EP1061108A3 publication Critical patent/EP1061108A3/en
Application granted granted Critical
Publication of EP1061108B1 publication Critical patent/EP1061108B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/683Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L21/6835Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L21/6836Wafer tapes, e.g. grinding or dicing support tapes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/20Adhesives in the form of films or foils characterised by their carriers
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/30Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38Pressure-sensitive adhesives [PSA]
    • C09J7/381Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385Acrylic polymers
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/31Applications of adhesives in processes or use of adhesives in the form of films or foils as a masking tape for painting
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2221/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
    • H01L2221/67Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
    • H01L2221/683Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L2221/68304Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L2221/68327Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support used during dicing or grinding
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/14Layer or component removable to expose adhesive
    • Y10T428/1452Polymer derived only from ethylenically unsaturated monomer
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/14Layer or component removable to expose adhesive
    • Y10T428/1462Polymer derived from material having at least one acrylic or alkacrylic group or the nitrile or amide derivative thereof [e.g., acrylamide, acrylate ester, etc.]
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/28Web or sheet containing structurally defined element or component and having an adhesive outermost layer
    • Y10T428/2852Adhesive compositions
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/28Web or sheet containing structurally defined element or component and having an adhesive outermost layer
    • Y10T428/2852Adhesive compositions
    • Y10T428/287Adhesive compositions including epoxy group or epoxy polymer
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/28Web or sheet containing structurally defined element or component and having an adhesive outermost layer
    • Y10T428/2852Adhesive compositions
    • Y10T428/2878Adhesive compositions including addition polymer from unsaturated monomer
    • Y10T428/2891Adhesive compositions including addition polymer from unsaturated monomer including addition polymer from alpha-beta unsaturated carboxylic acid [e.g., acrylic acid, methacrylic acid, etc.] Or derivative thereof

Definitions

  • This invention relates to a technique for relieving staining on an adherend caused by re-peelable adhesive sheets to be used in manufacturing various industrial members, in particular, fine-processed parts such as semiconductors, circuits, various printed substrates, various masks and lead frames.
  • a desired circuit is formed by applying a resist material onto a silicon wafer, forming a resist pattern (resist film image) by a conventional photoprocessing technique, etching by using the pattern as a mask, and then removing the resist material which is unnecessary any more. Next, the application of the resist material is repeated to form the subsequent circuit. In case of forming circuits on various substrates, unnecessary resist materials are removed after the formation of resist patterns similar to the above process.
  • EP-A-0 947 553 discloses a pressure sensitive adhesive comprising a masticated isobutylene polymer, a release control agent and a carboxylic acid.
  • EP-A-0 819 746 discloses a curable pressure sensitive adhesive comprising a composition including a high molecular weight polymer, a compound containing an epoxy group and a polymerization initiator.
  • US-A- 4,181,635 discloses a pressure sensitive adhesive composition comprising a low molecular weight polyisoprene, an elastomer and a tackyfying resin.
  • an object of the invention is to provide a low-staining adhesive sheet capable of protecting the surface of adherend (for example, substrate) from contamination with organic staining matters originating in the adhesive sheet, when employed as a re-peelable adhesive sheet, for example, for removing a resist material or foreign matters, or for use as a surface-protector, masking material or the like.
  • Another object of the invention is to provide a method for removing a resist material by using this adhesive sheet.
  • the inventors have conducted intensive studies to achieve these objects. As a result, they have clarified that these organic staining matters remaining on the surface of adherend after peeling the adhesive sheet originate in a pressure-sensitive adhesive polymer (for example, acrylic polymer) contained as the main component in the adhesive layer. That is to say, because of having a broad distribution range of molecular weight and containing a large amount of oligomeric low-molecular weight matters, this pressure-sensitive adhesive polymer is liable to undergo breakage or cohesive failure, thereby causing the adherend contamination with organic matters.
  • a pressure-sensitive adhesive polymer for example, acrylic polymer
  • the inventors have found out that, when the adhesive layer in the adhesive sheet provided with the adhesive layer containing as the main component a pressure-sensitive adhesive polymer on a base film is substantially free from oligomeric low-molecular weight matters at least in the step of peeling the sheet, then the pressure-sensitive adhesive polymer undergoes neither breakage nor cohesive failure and thus the adherend can be protected from contamination with organic matters.
  • the inventors have conducted further studies and, as a result, found out that the adherend contamination with organic matters can be largely relieved by reducing the content of low-molecular weight matters and narrowing the distribution range of molecular weight by, for example, reprecipitating the pressure-sensitive adhesive polymer from a poor solvent, thereby completing the invention.
  • the inventors have further found out that the adherend contamination with organic matters can be largely relieved by effectively crosslinking the pressure-sensitive adhesive polymer (involving the low-molecular weight matters) by blending a polyfunctional compound therewith so as to give a gel fraction of at least 90%, as another means for solving the object, thereby completing the invention.
  • the invention provides a low-staining adhesive sheet as defined in claim 1.
  • Prefered embodiments are defined in claims 2 to 8. Further the present invention provides a method as defined in claim 9.
  • the pressure-sensitive adhesive polymer is substantially free from low-molecular weight matters having a molecular weight of 5,000 or less.
  • the pressure-sensitive adhesive polymer has a degree of molecular weight distribution (weight-average molecular weight/number-average molecular weight) of 10 or less.
  • the low-staining adhesive sheet contains a pressure-sensitive adhesive polymer which has been reprecipitated from a poor solvent and the low-staining adhesive sheet comprises an adhesive layer which contains, in addition to the pressure-sensitive adhesive polymer, a polyfunctional compound for crosslinking the pressure-sensitive adhesive polymer.
  • the invention further provides a prefered low-staining adhesive sheet wherein the pressure-sensitive adhesive polymer has been crosslinked so as to give a gel fraction of at least 90% and is substantially free from oligomeric low-molecular weight matters and a prefered low-staining adhesive sheet which have been designed to give a gel fraction of at least 95%.
  • the low-staining adhesive sheet contains a pressure-sensitive adhesive polymer which is an acrylic polymer containing as the main monomer an alkyl (meth)acrylate.
  • a pressure-sensitive adhesive polymer which is an acrylic polymer containing as the main monomer an alkyl (meth)acrylate.
  • the adhesive layer contains, in addition to the pressure-sensitive adhesive polymer, a polymerizable compound having at least one unsaturated double bond in its molecule and a polymerization initiator and further prefered is the low-staining adhesive sheet wherein the polymerization initiator is a photopolymerization initiator and the adhesive layer is a photocuring one.
  • the invention provides the low-staining adhesive sheet to be re-peeled for removing a resist material and foreign matters, and for use as a re-peeling surface-protector, masking material, or the like and a method for removing a resist material which comprises adhering the low-staining adhesive sheet to an article having a resist pattern, curing the low-staining adhesive sheet in case of a curing one, and then removing the resist material together with the sheet from the article by a peeling procedure.
  • the "gel fraction" as used herein means a value measured after curing the adhesive sheet under definite conditions.
  • the base film to be used in the invention are plastic films comprising, for example, polyethylene, polypropylene, polyethylene terephthalate or acetyl cellulose and usually having a thickness of from 10 to 100 ⁇ m.
  • the adhesive layer to be formed on the base film is a photocuring one as will be described hereinafter, a plastic film permeable to light, for example, ultraviolet rays may be appropriately selected therefor.
  • an adhesive layer usually having a thickness of 10 to 180 ⁇ m is formed on the base film to give an adhesive sheet in the form of a sheet or a tape.
  • This adhesive layer contains as the main component a pressure-sensitive adhesive polymer.
  • the pressure-sensitive adhesive polymer is an acrylic polymer containing an alkyl (meth)acrylate as the main monomer therefor.
  • Such an acrylic polymer can be synthesized by using, as the main monomer, an alkyl (meth)acrylate, namely, an acrylic acid or methacrylic acid ester of an alcohol usually having not more than 12 carbon atoms (for example, n-butyl acrylate, 2-ethylhexyl acrylate), optionally together with a carboxyl- or hydroxyl-containing monomer (for example, acrylic acid, methacrylic acid, hydroxyethyl acrylate) or another modifying monomer (for example, vinyl acetate, vinyl propionate, styrene, acrylonitrile, acrylamide, glycidyl acrylate) and polymerizing these monomers by conventional methods such as solution polymerization, emulsion polymerization, suspension polymerization or bulk polymerization.
  • an alkyl (meth)acrylate namely, an acrylic acid or methacrylic acid ester of an alcohol usually having not more than 12 carbon atoms (for example, n-but
  • the acrylic polymer thus synthesized generally has a broad molecular weight distribution range.
  • the acrylic polymer is in the form of mixtures containing various components over a broad range from oligomers having a molecular weight of not more than several thousands to polymers having a molecular weight of several millions and the content of the oligomers having a molecular weight of not more than several thousands amounts to several % to 10% by weight.
  • a characteristic of the invention resides in that a pressure-sensitive adhesive polymer typified by such an acrylic polymer is reprecipitated from a poor solvent so that it becomes substantially free from low-molecular weight matters having a molecular weight of 5,000 or less, preferably 10,000 or less. It is defined that the degree of molecular weight distribution (weight-average molecular weight/number-average molecular weight) is 10 or less, preferably 8 or less and still preferably 5 or less (but not less than 2 in usual).
  • the reprecipitation is a treatment which is carried out in the following manner.
  • a solvent in which the polymer shows a low solubility for example, alcoholic solvents such as methanol, ethanol or isopropyl alcohol, or aliphatic hydrocarbon solvents such as hexane or petroleum ether
  • the poor solvent for example, alcoholic solvents such as methanol, ethanol or isopropyl alcohol, or aliphatic hydrocarbon solvents such as hexane or petroleum ether
  • the resultant mixture is allowed to stand at a room temperature or a low temperature and then the polymer thus reprecipitated is recovered and dried.
  • the method for the recovery of the low-molecular weight matters in the polymer is not restricted to this reprecipitation treatment but various publicly known methods may be employed therefor.
  • a pressure-sensitive adhesive polymer having been subjected to the reprecipitation treatment as described above contains little low-molecular weight matters having a molecular weight of 5,000 or less, thereby being appropriately us
  • a low-staining adhesive sheet which is free from the problem of the contamination of the adherend surface due to organic matters remaining thereon, as observed conventionally, and can be appropriately usable as a re-peelable sheet, can be obtained by using a pressure-sensitive adhesive polymer substantially free from low-molecular weight matters having a molecular weight of 5,000 or less and by using the polymer having a narrow molecular weight distribution range, i.e., a degree of molecular weight distribution of 10 or less.
  • the pressure-sensitive adhesive polymer to be used in the invention has a weight-average molecular weight of from 500,000 to 5,000,000 and a number-average molecular weight of form 300,000 to 3,000,000. These average molecular weights and degree of molecular weight distribution are expressed in data determined by the gel permeation chromatography (GPC) method in terms of polystyrene. It can be confirmed on the basis of a molecular weight distribution curve whether or not the polymer contains low-molecular weight matters having a molecular weight of 5,000 or less.
  • GPC gel permeation chromatography
  • the pressure-sensitive adhesive polymer further contains a polyfunctional compound such as a polyisocyanate compound, a polyfunctional epoxy compound or an aziridine compound to thereby elevate the cohesive force.
  • a polyfunctional compound such as a polyisocyanate compound, a polyfunctional epoxy compound or an aziridine compound to thereby elevate the cohesive force.
  • a polyfunctional compound is preliminarily added to the adhesive layer and the pressure-sensitive adhesive polymer is crosslinked by reacting the polyfunctional compound with the carboxyl or hydroxyl group in the pressure-sensitive adhesive polymer molecule in the step of forming the adhesive layer on the base film (i.e., the drying step following the application or the subsequent heating step).
  • the low-molecular weight components contained in the polymer are allowed to sufficiently participate in the crosslinking reaction so as to give a gel fraction of at least 90%, preferably at least 95%.
  • a pressure-sensitive adhesive polymer substantially free from oligomeric low-molecular weight matters can be obtained.
  • polyfunctional compound usable in the invention examples include polyfunctional epoxy compounds, polyisocyanate compounds and aziridine compounds. It is also favorable to use a combination of two or more polyfunctional compounds to thereby achieve sufficient crosslinkage.
  • the amount of the polyfunctional compound may be appropriately determined so as to give a gel fraction of at least 90%, preferably at least 95%. It is usually recommended to use from 0.1 to 3 parts by weight, preferably from 2 to 10 parts by weight, of the polyfunctional compound per 100 parts by weight of the pressure-sensitive adhesive polymer.
  • the adhesive layer in the invention use may be made of various ones containing the specific pressure-sensitive adhesive polymer as described above as the main component. It is preferable to use a curing adhesive layer which contains, in addition to the pressure-sensitive adhesive polymer as described above as the main component, a polymerizable compound having at least one unsaturated double bond in its molecule and a polymerization initiator. It is particularly preferable that the polymerization initiator is a photopolymerization initiator and the adhesive layer is a photocuring one.
  • the polymerizable compound as described above is a nonvolatile compound having at least one unsaturated double bond in its molecule which can be cured by applying light or heat energy thereto.
  • examples thereof include phenoxypolyethylene glycol (meth)acrylate, ⁇ -caprolactone (meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, urethane (meth)acrylate, epoxy (meth)acrylate and oligoester (meth)acrylate. Either one of these compounds or a mixture of two or more thereof may be used. It is recommended that the polymerizable compound is used in an amount of from 10 to 400 parts by weight, preferably from 50 to 300 parts by weight, per 100 parts by weight of the pressure-sensitive adhesive polymer.
  • polymerization initiator as described above, use may be made of photopolymerization initiators capable of liberating a radical upon light irradiation, for example, benzyl dimethyl ketal, benzoin, benzoin ethyl ether and dibenzyl. It is also possible to use therefor polymerization initiators capable of liberating a radical upon application of heat energy, for example, organic peroxides such as benzoyl peroxide and azo initiators such as 2,2'-azobisisobutyronitrile. It is recommended that the polymerization initiator is used in an amount of from 0.1 to 10 parts by weight, preferably from 1 to 5 parts by weight, per 100 parts by weight of the pressure-sensitive adhesive polymer.
  • These adhesive layers of various types may further contain various publicly known additives such as tackifiers, colorants and aging inhibitors, so long as the effects of the invention are not damaged thereby.
  • the low-staining adhesive sheet of the invention having the constitution as described above is usable for various purposes, for example, in removing resist materials and foreign matters in the processes of manufacturing various industrial members, in particular, fine-processed parts such as semiconductors, circuits, various printed substrates, various masks and lead frames, and in re-peeling various substances other than those cited above, thereby contributing to the relief of adherend contamination.
  • this adhesive sheet is widely usable in various cases wherein the adhesive sheet is to be peeled during or after using, for example, surface-protecting, masking, and other re-peeling purposes.
  • a method for removing a resist material is provided as an invention pertaining to a method for using the low-staining adhesive sheet as described above.
  • the low-staining adhesive sheet as described above is adhered, under heating and/or pressing if necessary, to an article having a resist pattern to thereby combine the adhesive layer with the resist material.
  • the resist material is removed together with the low-staining adhesive sheet from the article by a peeling procedure.
  • the removal method as described above can be easily carried out. Moreover, this method is free from fears of pollution of the working environment, injection of impurities contained in the resist material into wafers, or damage of semiconductor substrates. In this case, furthermore, no organic staining matter originating in the low-staining adhesive sheet remains on the article surface and thus no procedure for removing staining matters is needed after peeling the low-staining adhesive sheet. Thus, the resist material can be very conveniently removed thereby.
  • a resist film image A means one formed on a semiconductor wafer in accordance with the method of Referential Example 1.
  • a resist composed of PHS (polyhydroxystyrene derivative) and an acid-generating agent was applied onto the surface of a silicon wafer (8 inch-semiconductor substrate) having an oxide film formed on the surface thereof. After forming a pattern by heating, exposing to light and developing, the oxide film was removed by dry etching with the use of the resist pattern as a mask.
  • the resist pattern on the thus processed silicon wafer was referred to as the resist film image A.
  • This acrylic polymer B which had been thus reprecipitated from the poor solvent, showed Mw of 380,000 and Mw/Mn of 3.0. Based on the molecular weight distribution curve, it was found out that this acrylic polymer B was completely free from low-molecular weight matters having a molecular weight of 50,000 or less.
  • the low-staining adhesive sheet obtained above was adhered to the resist film image A on a silicon wafer by using pressure rollers under heating. Then it was irradiated with ultraviolet rays at a dose of 1,000 mJ/cm 2 by using a high-pressure mercury lamp to cure the adhesive sheet. Subsequently, the adhesive sheet was peeled together with the resist film image A so as to completely remove the image A from the silicon wafer. When observed under a microscope, the resist had been completely removed from the silicon wafer and no organic staining matter originating in the adhesive layer was found out.
  • An adhesive solution was prepared as in Example 1 but using 100 g (in terms of solid matters) of the acrylic polymer A before the reprecipitation from a poor solvent as a substitute for the acrylic polymer B.
  • an adhesive sheet was prepared as in Example 1.
  • the resist film image A was peeled as in Example 1 but using the thus obtained adhesive sheet.
  • the resist had been mostly removed from the silicon wafer but organic staining matters originating in the adhesive layer remained thereon.
  • the solution thus obtained was applied onto a base film made of a polyester film of 50 ⁇ m in thickness and dried in a drying oven at 130°C for 3 minutes to form a crosslinked photocuring adhesive layer of 35 ⁇ m in thickness.
  • a low-staining adhesive sheet was obtained.
  • the gel fraction of the adhesive layer of this low-staining adhesive sheet was measured in the following manner.
  • the photocuring adhesive layer of 35 ⁇ m in thickness was irradiated with ultraviolet rays at a dose of 1,000 mJ/cm 2 by using a high-pressure mercury lamp to cure the adhesive layer.
  • a 15.0 g portion of the adhesive layer was introduced into 500 ml of ethyl acetate and stirred therein at 60°C for 10 hours.
  • the insoluble matters were filtered off and the filtrate was concentrated in a rotary evaporator and dried under reduced pressure (1 mmHg, 1 hour) to thereby completely remove the ethyl acetate.
  • the obtained concentrate weighed 0.3 g. Therefore, the weight of the adhesive having been filtered off corresponded to 14.7 g and thus the gel fraction calculated therefrom was 98%.
  • the resist film image A was peeled as in Example 1.
  • the resist had been completely removed from the silicon wafer and no organic staining matter originating in the adhesive layer was found out.
  • the gel fraction of the photocuring adhesive layer of this low-staining adhesive sheet measured as in Example 3 was 99%.
  • the resist film image A was peeled as in Example 1. When observed under a microscope, the resist had been completely removed from the silicon wafer and no organic staining matter originating in the adhesive layer was found out.
  • a low-staining adhesive sheet was prepared as in Example 3 but using no polyepoxy compound in the solution to be applied onto the base film.
  • the gel fraction of the photocuring adhesive layer of this low-staining adhesive sheet measured as in Example 3 was 88%.
  • the resist film image A was peeled as in Example 1. When observed under a microscope, the resist had been mostly removed from the silicon wafer and but organic staining matters originating in the adhesive layer remained thereon.
  • the invention can provide a low-staining adhesive sheet which gives no organic staining matters remaining on the surface of article (for example, substrate) to be used as an adherend and is useful in removing resist materials and foreign matters, and re-peeling surface-protectors, masking materials, and other materials.
  • the invention further provides a method for conveniently peeling and removing resist materials on articles by using this low-staining adhesive sheet.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
EP00112397A 1999-06-10 2000-06-09 Low-staining adhesive sheets and method for removing resist material Expired - Lifetime EP1061108B1 (en)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP16385799 1999-06-10
JP16385799 1999-06-10
JP36778599A JP4495813B2 (ja) 1999-12-24 1999-12-24 低汚染性接着シ―ト類とレジスト材の除去方法
JP36778599 1999-12-24
JP2000011094 2000-01-20
JP2000011094A JP4859005B2 (ja) 1999-06-10 2000-01-20 低汚染性接着シ―ト類とレジスト材の除去方法

Publications (3)

Publication Number Publication Date
EP1061108A2 EP1061108A2 (en) 2000-12-20
EP1061108A3 EP1061108A3 (en) 2001-05-16
EP1061108B1 true EP1061108B1 (en) 2003-10-22

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EP00112397A Expired - Lifetime EP1061108B1 (en) 1999-06-10 2000-06-09 Low-staining adhesive sheets and method for removing resist material

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JP3710368B2 (ja) * 2000-09-25 2005-10-26 シャープ株式会社 積層フィルムの製造方法
JP2002231600A (ja) * 2001-01-30 2002-08-16 Nitto Denko Corp レジスト除去用接着テープとレジスト除去方法
WO2004069951A1 (ja) * 2003-02-05 2004-08-19 The Furukawa Electric Co., Ltd. ウエハ貼着用粘着テープ
WO2005005501A1 (en) * 2003-06-18 2005-01-20 Adhesives Research, Inc. Heat releasable wafer dicing tape
JP4880877B2 (ja) * 2004-01-16 2012-02-22 リンテック株式会社 フレキシブルプリント配線基板の製造方法及び該製造方法に用いる再剥離性剥離材付き工程フィルム
WO2007029936A1 (en) * 2005-09-05 2007-03-15 Lg Chem, Ltd. Acrylic pressure-sensitive adhesive composition for polarizing film
JP5497276B2 (ja) * 2008-07-08 2014-05-21 東京応化工業株式会社 接着剤組成物の製造方法
JP5537789B2 (ja) 2008-10-01 2014-07-02 日東電工株式会社 レーザー加工用粘着シート及びレーザー加工方法
US20120103016A1 (en) * 2010-11-01 2012-05-03 Ippolita Rostagno Custom stones and methods for producing custom stones for jewelry
CN108174616B (zh) * 2015-10-05 2022-03-29 琳得科株式会社 半导体加工用片
CN110527445A (zh) * 2019-09-17 2019-12-03 昆山久庆新材料科技有限公司 一种高持粘力的交联型压敏胶及其制备方法
EP4169994A1 (en) 2021-10-25 2023-04-26 Nitto Belgium NV Pressure-sensitive adhesive composition and surface protection sheets comprising the same

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US6602599B1 (en) 2003-08-05
EP1061108A3 (en) 2001-05-16
KR100618749B1 (ko) 2006-09-04
KR20010007330A (ko) 2001-01-26
DE60006035T2 (de) 2004-05-19
EP1061108A2 (en) 2000-12-20
TW567221B (en) 2003-12-21
DE60006035D1 (de) 2003-11-27

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